W Roshantha Perera, Aafreen Ansari, Cameron Nowell, Benjamin Geiger, Nicolas H Voelcker, Jessica E Frith, Victor J Cadarso
Understanding cellular response to mechanical cues in three‐dimensional (3D) environments remains a central challenge in cell biology. Shape and force distribution are key regulators of mechanosensing. In vivo, cells are embedded in 3D environments where force transmission and cytoskeletal behavior differ markedly from two‐dimensional systems. However, current tools lack the resolution to precisely control single‐cell geometry or quantify traction forces in defined 3D contexts. Here, a direct laser writing‐based platform is presented that fabricates microscale cage structures capable of confining individual mesenchymal stem cells in defined 3D geometries while enabling high‐resolution traction force measurements. The system allows independent control of cell volume and shape, and captures nanowire deflection as a readout of cell‐generated forces at varying heights. Using this platform, this study reveals that 3D shape alone, modulates cytoskeletal organization, contractility, and localization of the mechanosensitive transcription factor Yes‐associated protein (YAP) in a shape and time dependent manner. Square cages induced previously unreported vertical actin fibers and corner‐enriched myosin accumulation, suggesting that pointed 3D geometry alters internal force distribution. Delayed YAP nuclear translocation indicates a time‐sensitive mechanotransduction response to 3D confinement. Altogether, this platform offers a tunable 3D confinement tool and new insights into how shape alone direct cellular force architecture and mechanosensitive signaling.
{"title":"Two‐Photon Polymerized 3D Geometries to Study Single‐Cell Mechanotransduction and Force Generation in Mesenchymal Stromal Cells","authors":"W Roshantha Perera, Aafreen Ansari, Cameron Nowell, Benjamin Geiger, Nicolas H Voelcker, Jessica E Frith, Victor J Cadarso","doi":"10.1002/smll.202508899","DOIUrl":"https://doi.org/10.1002/smll.202508899","url":null,"abstract":"Understanding cellular response to mechanical cues in three‐dimensional (3D) environments remains a central challenge in cell biology. Shape and force distribution are key regulators of mechanosensing. In vivo, cells are embedded in 3D environments where force transmission and cytoskeletal behavior differ markedly from two‐dimensional systems. However, current tools lack the resolution to precisely control single‐cell geometry or quantify traction forces in defined 3D contexts. Here, a direct laser writing‐based platform is presented that fabricates microscale cage structures capable of confining individual mesenchymal stem cells in defined 3D geometries while enabling high‐resolution traction force measurements. The system allows independent control of cell volume and shape, and captures nanowire deflection as a readout of cell‐generated forces at varying heights. Using this platform, this study reveals that 3D shape alone, modulates cytoskeletal organization, contractility, and localization of the mechanosensitive transcription factor Yes‐associated protein (YAP) in a shape and time dependent manner. Square cages induced previously unreported vertical actin fibers and corner‐enriched myosin accumulation, suggesting that pointed 3D geometry alters internal force distribution. Delayed YAP nuclear translocation indicates a time‐sensitive mechanotransduction response to 3D confinement. Altogether, this platform offers a tunable 3D confinement tool and new insights into how shape alone direct cellular force architecture and mechanosensitive signaling.","PeriodicalId":228,"journal":{"name":"Small","volume":"29 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lei Wang, Xin Ma, Tong Chen, Cheng Yuan, Tianran Yan, Pan Zeng, Liang Zhang
Vacancy engineering has emerged as an efficient approach for constructing high‐performance electrocatalysts to enhance lithium polyselenides (LiPSes) adsorption and conversion in lithium−selenium (Li−Se) batteries. However, the catalytic mechanisms of vacancies remain one‐sided because of the insufficient understanding of the dynamic evolution of electrocatalysts during reactions. Herein, by leveraging MoS 2 with sulfur vacancies (SVs‐MoS 2 ) as a model electrocatalyst, the phase reconstruction of defective electrocatalysts during LiPSes redox reactions, and the essence of enhanced electrocatalytic activity are unveiled. As validated by comprehensive experimental characterizations and theoretical calculations, the interaction between LiPSes and SVs‐MoS 2 is demonstrated to induce the in situ topotactic transformation from SVs‐MoS 2 to MoSSe. This compositional evolution affords an optimized d‐p orbital hybridization, which not only facilitates the intrinsic charge transfer but also activates the basal‐plane catalytic activity though the electron‐rich Se sites, thereby expediting the LiPSes redox kinetics. Benefitting from these advantages, the Li−Se batteries assembled with SVs‐MoS 2 exhibit an outstanding capacity retention and cycling stability at a wide temperature range (−10–40 °C). This work sheds light on the topotactic reconstruction of defective electrocatalysts during the electrochemical reactions, which helps attain the fundamental understanding and extend the applications of vacancy engineering in electrocatalysis.
空位工程已成为构建高性能电催化剂以增强锂硒（Li−Se）电池中聚硒化锂（LiPSes）的吸附和转化的有效方法。然而，由于对电催化剂在反应过程中的动态演化认识不足，空位的催化机理仍然是片面的。本文利用含硫空位的MoS 2 （SVs - MoS 2）作为模型电催化剂，揭示了缺陷电催化剂在LiPSes氧化还原反应中的相重构，以及增强电催化活性的本质。综合实验表征和理论计算证实，LiPSes与SVs - MoS 2之间的相互作用诱导了SVs - MoS 2向MoSSe的原位拓扑转化。这种成分演化提供了优化的d - p轨道杂化，这不仅促进了内在电荷转移，而且通过富电子Se位点激活了基面催化活性，从而加快了LiPSes氧化还原动力学。受益于这些优点，用SVs - MoS 2组装的Li - Se电池在宽温度范围（- 10-40°C）下表现出出色的容量保持和循环稳定性。本研究揭示了电化学反应过程中缺陷电催化剂的拓扑结构重构，有助于对空位工程在电催化中的基本认识和应用的拓展。
{"title":"Vacancy‐Induced In Situ Topotactic Transformation of MoS 2 for Enhanced Polyselenide Catalytic Conversion","authors":"Lei Wang, Xin Ma, Tong Chen, Cheng Yuan, Tianran Yan, Pan Zeng, Liang Zhang","doi":"10.1002/smll.202511666","DOIUrl":"https://doi.org/10.1002/smll.202511666","url":null,"abstract":"Vacancy engineering has emerged as an efficient approach for constructing high‐performance electrocatalysts to enhance lithium polyselenides (LiPSes) adsorption and conversion in lithium−selenium (Li−Se) batteries. However, the catalytic mechanisms of vacancies remain one‐sided because of the insufficient understanding of the dynamic evolution of electrocatalysts during reactions. Herein, by leveraging MoS <jats:sub>2</jats:sub> with sulfur vacancies (SVs‐MoS <jats:sub>2</jats:sub> ) as a model electrocatalyst, the phase reconstruction of defective electrocatalysts during LiPSes redox reactions, and the essence of enhanced electrocatalytic activity are unveiled. As validated by comprehensive experimental characterizations and theoretical calculations, the interaction between LiPSes and SVs‐MoS <jats:sub>2</jats:sub> is demonstrated to induce the in situ topotactic transformation from SVs‐MoS <jats:sub>2</jats:sub> to MoSSe. This compositional evolution affords an optimized d‐p orbital hybridization, which not only facilitates the intrinsic charge transfer but also activates the basal‐plane catalytic activity though the electron‐rich Se sites, thereby expediting the LiPSes redox kinetics. Benefitting from these advantages, the Li−Se batteries assembled with SVs‐MoS <jats:sub>2</jats:sub> exhibit an outstanding capacity retention and cycling stability at a wide temperature range (−10–40 °C). This work sheds light on the topotactic reconstruction of defective electrocatalysts during the electrochemical reactions, which helps attain the fundamental understanding and extend the applications of vacancy engineering in electrocatalysis.","PeriodicalId":228,"journal":{"name":"Small","volume":"47 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymer grafting density is a critical parameter in regulating nanoparticle self‐assembly, as precise control over it enables programmable design of nanostructures. In this study, a novel quartz crystal microbalance (QCM)‐based method is developed for in situ monitoring of the grafting kinetics of poly(N‐isopropylacrylamide) (PNIPAM) onto gold nanoparticles (AuNPs). Experimental results show that during the initial grafting stage (t = 360 s), a grafting rate constant ( k1 ) of 1.06 × 10 −2 chains nm −2 s −1 and a diffusion‐controlled mechanism can be observed. As grafting proceeds, the polymer chains adopt an extended conformation, resulting in a slower grafting rate. Isothermal titration calorimetry (ITC) measurements further validated the reliability of the QCM approach. Further investigations revealed the significant influence of polymer chain length, interparticle spacing, and temperature on grafting behavior. In situ small‐angle X‐ray scattering (SAXS) studies demonstrated that grafting density plays a decisive role in determining the assembly structures: long‐chain PNIPAM grafted at low density forms random close‐packed (RCP) structure, while high grafting density promotes face‐centered cubic (FCC) ordering. This work not only establishes an in situ method for monitoring grafting on AuNPs, but also clarifies polymer density‐structure relationships for nanomaterial design.
{"title":"Real‐Time Investigation of PNIPAM Grafting Dynamics and Grafting Density‐Dependent Assembly of Gold Nanoparticles","authors":"Rui Ren, Bijin Xiong, Jintao Zhu","doi":"10.1002/smll.202512449","DOIUrl":"https://doi.org/10.1002/smll.202512449","url":null,"abstract":"Polymer grafting density is a critical parameter in regulating nanoparticle self‐assembly, as precise control over it enables programmable design of nanostructures. In this study, a novel quartz crystal microbalance (QCM)‐based method is developed for in situ monitoring of the grafting kinetics of poly(N‐isopropylacrylamide) (PNIPAM) onto gold nanoparticles (AuNPs). Experimental results show that during the initial grafting stage (t = 360 s), a grafting rate constant ( <jats:italic>k</jats:italic> <jats:sub>1</jats:sub> ) of 1.06 × 10 <jats:sup>−2</jats:sup> chains nm <jats:sup>−</jats:sup> <jats:sup>2</jats:sup> s <jats:sup>−1</jats:sup> and a diffusion‐controlled mechanism can be observed. As grafting proceeds, the polymer chains adopt an extended conformation, resulting in a slower grafting rate. Isothermal titration calorimetry (ITC) measurements further validated the reliability of the QCM approach. Further investigations revealed the significant influence of polymer chain length, interparticle spacing, and temperature on grafting behavior. In situ small‐angle X‐ray scattering (SAXS) studies demonstrated that grafting density plays a decisive role in determining the assembly structures: long‐chain PNIPAM grafted at low density forms random close‐packed (RCP) structure, while high grafting density promotes face‐centered cubic (FCC) ordering. This work not only establishes an in situ method for monitoring grafting on AuNPs, but also clarifies polymer density‐structure relationships for nanomaterial design.","PeriodicalId":228,"journal":{"name":"Small","volume":"23 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The direct integration of high‐performance ferroelectric oxides with silicon remains challenging due to lattice mismatch, thermal incompatibility, and the need for high‐temperature epitaxial growth. Here, a hybrid integration approach is demonstrated in which crystalline BaTiO 3 (BTO) membranes are first transferred onto Pt‐coated Si substrates and subsequently used as vector substrates (VS) for the growth of epitaxial (001) Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) thin films via chemical solution deposition (CSD). A KI + HCl based etchant enables rapid and complete dissolution of the SrVO 3 sacrificial layer in ≈30 min, reducing the release time from days to minutes compared with conventional water‐based approaches to dissolve AVO 3 /AMoO 3 (A = Ca, Sr, Ba). The BTO VS imposes dominant (00l) out‐of‐plane orientation and in‐plane cube‐on‐cube epitaxy in the overlying PZT. Devices exhibit P r ≈ 10–12 µC cm −2 and E C ≈ 100 kV cm −1 , with stable switching to 10⁸ cycles on the VS. From piezoelectric butterfly loops, the study extracts ≈ 70 pm V −1 for PZT on VS and ≈54 pm V −1 for PZT grown on conventional Pt‐Si substrates. The approach establishes a general pathway for transferring crystalline oxides to any arbitrary substrate and employing them as vector substrates for epitaxial integration of functional oxides.
由于晶格失配、热不相容以及对高温外延生长的需要，高性能铁电氧化物与硅的直接集成仍然具有挑战性。本文展示了一种混合集成方法，其中晶体batio3 （BTO）膜首先转移到Pt涂层的Si衬底上，然后通过化学溶液沉积（CSD）作为矢量衬底（VS）生长外延（001）Pb(Zr 0.52 Ti 0.48) o3 （PZT）薄膜。KI + HCl基蚀刻剂可以在约30分钟内快速完全溶解srvo3牺牲层，与传统的水基方法溶解AVO 3 / amoo3 （A = Ca, Sr, Ba）相比，将释放时间从几天缩短到几分钟。BTO VS在覆盖的PZT上施加了显性（00l）面外取向和面内立方体对立方体外延。器件表现出P r≈10 - 12µC cm - 2和E C≈100 kV cm - 1，在VS上稳定地切换到10⁸循环。从压电蝴蝶环中，研究得到VS上PZT的≈70 pm V - 1，而在传统Pt - Si衬底上生长的PZT的≈54 pm V - 1。该方法建立了将晶体氧化物转移到任意衬底的一般途径，并将其用作功能氧化物外延集成的矢量衬底。
{"title":"A Facile Vector Substrate Platform via BaTiO 3 Membrane Transfer Enables High‐Quality Solution‐Processed Epitaxial PZT on Silicon","authors":"Asraful Haque, Antony Jeyaseelan, Shubham Kumar Parate, Srinivasan Raghavan, Pavan Nukala","doi":"10.1002/smll.202511406","DOIUrl":"https://doi.org/10.1002/smll.202511406","url":null,"abstract":"The direct integration of high‐performance ferroelectric oxides with silicon remains challenging due to lattice mismatch, thermal incompatibility, and the need for high‐temperature epitaxial growth. Here, a hybrid integration approach is demonstrated in which crystalline BaTiO <jats:sub>3</jats:sub> (BTO) membranes are first transferred onto Pt‐coated Si substrates and subsequently used as vector substrates (VS) for the growth of epitaxial (001) Pb(Zr <jats:sub>0.52</jats:sub> Ti <jats:sub>0.48</jats:sub> )O <jats:sub>3</jats:sub> (PZT) thin films via chemical solution deposition (CSD). A KI + HCl based etchant enables rapid and complete dissolution of the SrVO <jats:sub>3</jats:sub> sacrificial layer in ≈30 min, reducing the release time from days to minutes compared with conventional water‐based approaches to dissolve AVO <jats:sub>3</jats:sub> /AMoO <jats:sub>3</jats:sub> (A = Ca, Sr, Ba). The BTO VS imposes dominant (00l) out‐of‐plane orientation and in‐plane cube‐on‐cube epitaxy in the overlying PZT. Devices exhibit P <jats:sub>r</jats:sub> ≈ 10–12 µC cm <jats:sup>−2</jats:sup> and E <jats:sub>C</jats:sub> ≈ 100 kV cm <jats:sup>−1</jats:sup> , with stable switching to 10⁸ cycles on the VS. From piezoelectric butterfly loops, the study extracts ≈ 70 pm V <jats:sup>−1</jats:sup> for PZT on VS and ≈54 pm V <jats:sup>−1</jats:sup> for PZT grown on conventional Pt‐Si substrates. The approach establishes a general pathway for transferring crystalline oxides to any arbitrary substrate and employing them as vector substrates for epitaxial integration of functional oxides.","PeriodicalId":228,"journal":{"name":"Small","volume":"27 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jasmin Helgert, Jana Timm, Lion Schumacher, Roland Marschall
A novel quick and facile polymer‐assisted microwave synthesis route to prepare mesoporous binary metal oxides α‐Fe 2 O 3 and α‐Mn 2 O 3 and spinel‐type ferrites NiFe 2 O 4 and ZnFe 2 O 4 is presented, which can potentially be applied for many other mixed metal oxides. The presented synthesis only needs 15–30 min, much shorter than conventional approaches for mesoporous materials. Thorough characterization of the materials is performed by Powder X‐Ray Diffraction (PXRD), Raman spectroscopy, energy dispersive X‐ray spectroscopy (EDXS), nitrogen physisorption analysis, mercury intrusion porosimetry (MIP), diffuse reflectance infrared fourier transform (DRIFT) spectroscopy, UV–Vis‐spectroscopy, X‐Ray photoelectron spectroscopy (XPS), and scanning (SEM) as well as transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Furthermore, mesoporous α‐Mn 2 O 3 and NiFe 2 O 4 are applied as electrocatalysts for electrocatalytic oxygen evolution in alkaline media, showing improved performance compared to nanoparticles or EISA‐derived mesoporous NiFe 2 O 4 .
{"title":"Polymer‐Assisted Direct and Rapid Microwave Synthesis of Mesoporous Binary and Ternary Metal Oxides for Electrocatalytic Water Oxidation","authors":"Jasmin Helgert, Jana Timm, Lion Schumacher, Roland Marschall","doi":"10.1002/smll.202510771","DOIUrl":"https://doi.org/10.1002/smll.202510771","url":null,"abstract":"A novel quick and facile polymer‐assisted microwave synthesis route to prepare mesoporous binary metal oxides α‐Fe <jats:sub>2</jats:sub> O <jats:sub>3</jats:sub> and α‐Mn <jats:sub>2</jats:sub> O <jats:sub>3</jats:sub> and spinel‐type ferrites NiFe <jats:sub>2</jats:sub> O <jats:sub>4</jats:sub> and ZnFe <jats:sub>2</jats:sub> O <jats:sub>4</jats:sub> is presented, which can potentially be applied for many other mixed metal oxides. The presented synthesis only needs 15–30 min, much shorter than conventional approaches for mesoporous materials. Thorough characterization of the materials is performed by Powder X‐Ray Diffraction (PXRD), Raman spectroscopy, energy dispersive X‐ray spectroscopy (EDXS), nitrogen physisorption analysis, mercury intrusion porosimetry (MIP), diffuse reflectance infrared fourier transform (DRIFT) spectroscopy, UV–Vis‐spectroscopy, X‐Ray photoelectron spectroscopy (XPS), and scanning (SEM) as well as transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Furthermore, mesoporous α‐Mn <jats:sub>2</jats:sub> O <jats:sub>3</jats:sub> and NiFe <jats:sub>2</jats:sub> O <jats:sub>4</jats:sub> are applied as electrocatalysts for electrocatalytic oxygen evolution in alkaline media, showing improved performance compared to nanoparticles or EISA‐derived mesoporous NiFe <jats:sub>2</jats:sub> O <jats:sub>4</jats:sub> .","PeriodicalId":228,"journal":{"name":"Small","volume":"87 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Neena Prasad, Asmita Dutta, Philip Nathaniel Immanuel, Daliya Melichov, Vojtech Kundrat, Raanan Carmieli, Achiad Goldreich, Akshay Puravankara, Ido Bar On, Arie Borenstein, Lena Yadgarov
Rapid industrialization and unlimited human activities have led to severe environmental challenges, particularly water contamination by persistent organic pollutants, posing serious risks to ecosystems and human health. Photocatalytic technology offers a sustainable remediation for pollutant degradation using solar energy. In this study, ultrathin carbon‐encapsulated ZnO nanoparticles, ZnO@C are employed, as an efficient photocatalyst, using methylene blue and methyl orange as model pollutants. The carbon has a favorable band alignment with ZnO for efficient charge transfer. In fact, the optical absorption studies and finite‐difference time‐domain simulations establish an enhanced absorption and light–matter interaction upon thin uniform carbon encapsulation. Photoluminescence quenching (≈80%) indicates reduced electron–hole recombination, facilitated by defect‐induced charge transfer from ZnO to carbon. Electron paramagnetic resonance measurements identify superoxide radicals (O 2 • − ) as the dominant reactive species, driving a selective radical‐mediated degradation pathway. Compared to pristine ZnO, the ZnO@C system exhibits over 60% higher degradation efficiency. Liquid chromatography–mass spectrometry analyses elucidate the sequential degradation pathway driven by O 2 • − . The ZnO@C demonstrates excellent photostability and reusability across multiple cycles, with a sixfold increase in kinetic rate constants over pristine ZnO. These improvements highlight the potential of ZnO@C core@shell nanostructures for sustainable environmental remediation.
{"title":"Highly Selective Photocatalytic Degradation of Organic Pollutants by ZnO@C Core–Shell Nanoparticles Via Superoxide Radical Pathway","authors":"Neena Prasad, Asmita Dutta, Philip Nathaniel Immanuel, Daliya Melichov, Vojtech Kundrat, Raanan Carmieli, Achiad Goldreich, Akshay Puravankara, Ido Bar On, Arie Borenstein, Lena Yadgarov","doi":"10.1002/smll.202508852","DOIUrl":"https://doi.org/10.1002/smll.202508852","url":null,"abstract":"Rapid industrialization and unlimited human activities have led to severe environmental challenges, particularly water contamination by persistent organic pollutants, posing serious risks to ecosystems and human health. Photocatalytic technology offers a sustainable remediation for pollutant degradation using solar energy. In this study, ultrathin carbon‐encapsulated ZnO nanoparticles, ZnO@C are employed, as an efficient photocatalyst, using methylene blue and methyl orange as model pollutants. The carbon has a favorable band alignment with ZnO for efficient charge transfer. In fact, the optical absorption studies and finite‐difference time‐domain simulations establish an enhanced absorption and light–matter interaction upon thin uniform carbon encapsulation. Photoluminescence quenching (≈80%) indicates reduced electron–hole recombination, facilitated by defect‐induced charge transfer from ZnO to carbon. Electron paramagnetic resonance measurements identify superoxide radicals (O <jats:sub>2</jats:sub> • <jats:sup>−</jats:sup> ) as the dominant reactive species, driving a selective radical‐mediated degradation pathway. Compared to pristine ZnO, the ZnO@C system exhibits over 60% higher degradation efficiency. Liquid chromatography–mass spectrometry analyses elucidate the sequential degradation pathway driven by O <jats:sub>2</jats:sub> • <jats:sup>−</jats:sup> . The ZnO@C demonstrates excellent photostability and reusability across multiple cycles, with a sixfold increase in kinetic rate constants over pristine ZnO. These improvements highlight the potential of ZnO@C core@shell nanostructures for sustainable environmental remediation.","PeriodicalId":228,"journal":{"name":"Small","volume":"252 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuqi Wang, Ya Li, Bin Yang, Hao Chen, Lu Han, Yuanyuan Cao, Yongsheng Li
Curvatures are fundamental parameters governing the topological changes and phase separations in soft matter systems. Explorations of Gaussian curvature, mean curvature, and their combination (as interfacial curvature linked to packing parameter) are essential for understanding the dynamic self‐assembly processes, especially for the critical and classic lamellar‐to‐bicontinuous transition. However, whether intermediate states arising from the changes in these curvatures exist remains a long‐standing controversy. Herein, this issue is addressed by identifying a unique saddle‐shaped hierarchical lamellar phase in a binary self‐assembly system containing polystyrene ‐b‐ poly(acrylic acid) (PS ‐b‐ PAA) and stearyltrimethylammonium bromide (STAB). This intermediate phase exhibits characteristics with negative Gaussian curvature similar to bicontinuous phase while maintaining lamellar topologies. Its existence attributes to the competing effects of the inserted STAB micelles imposed on PAA segments: electrostatic screening reduces PAA effective volume, while volume expansion increases it. This competition balance promotes the lamellae toward saddle‐shapes with enhanced molecular capacity and modulates their interfacial curvature to a critical intermediate value that is rarely stable in block copolymer systems. The thermostability of this intermediate phase serves as compelling evidence for the smooth interfacial curvature evolution pathway. This discovery provides insights into phase transformations in biological membranes, marking a significant advance in understanding complex soft matter systems.
曲率是控制软物质系统拓扑变化和相分离的基本参数。探索高斯曲率、平均曲率和它们的组合（作为与填料参数相关的界面曲率）对于理解动态自组装过程，特别是对于临界和经典的片层到双连续转变至关重要。然而，由这些曲率的变化引起的中间状态是否存在仍然是一个长期存在的争议。本文通过在含有聚苯乙烯- b -聚丙烯酸（PS - b - PAA）和硬脂基三甲基溴化铵（STAB）的二元自组装体系中确定一个独特的鞍形分层层状相来解决这个问题。这种中间相具有类似于双连续相的负高斯曲率特征，同时保持层状拓扑结构。它的存在是由于插入的STAB胶束施加在PAA片段上的竞争效应：静电筛选减少了PAA的有效体积，而体积膨胀增加了PAA的有效体积。这种竞争平衡促进了片层的鞍形，增强了分子容量，并将其界面曲率调节到一个临界的中间值，这在嵌段共聚物体系中很少稳定。这种中间相的热稳定性为光滑的界面曲率演化路径提供了令人信服的证据。这一发现提供了对生物膜相变的见解，标志着对复杂软物质系统的理解取得了重大进展。
{"title":"Evolution of Curvatures Between Lamellar and Bicontinuous Phases: Formation of Saddle‐Shaped Hierarchical Lamellar Structures in Binary Self‐Assembly System","authors":"Shuqi Wang, Ya Li, Bin Yang, Hao Chen, Lu Han, Yuanyuan Cao, Yongsheng Li","doi":"10.1002/smll.202508085","DOIUrl":"https://doi.org/10.1002/smll.202508085","url":null,"abstract":"Curvatures are fundamental parameters governing the topological changes and phase separations in soft matter systems. Explorations of Gaussian curvature, mean curvature, and their combination (as interfacial curvature linked to packing parameter) are essential for understanding the dynamic self‐assembly processes, especially for the critical and classic lamellar‐to‐bicontinuous transition. However, whether intermediate states arising from the changes in these curvatures exist remains a long‐standing controversy. Herein, this issue is addressed by identifying a unique saddle‐shaped hierarchical lamellar phase in a binary self‐assembly system containing polystyrene <jats:italic>‐b‐</jats:italic> poly(acrylic acid) (PS <jats:italic>‐b‐</jats:italic> PAA) and stearyltrimethylammonium bromide (STAB). This intermediate phase exhibits characteristics with negative Gaussian curvature similar to bicontinuous phase while maintaining lamellar topologies. Its existence attributes to the competing effects of the inserted STAB micelles imposed on PAA segments: electrostatic screening reduces PAA effective volume, while volume expansion increases it. This competition balance promotes the lamellae toward saddle‐shapes with enhanced molecular capacity and modulates their interfacial curvature to a critical intermediate value that is rarely stable in block copolymer systems. The thermostability of this intermediate phase serves as compelling evidence for the smooth interfacial curvature evolution pathway. This discovery provides insights into phase transformations in biological membranes, marking a significant advance in understanding complex soft matter systems.","PeriodicalId":228,"journal":{"name":"Small","volume":"23 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Habibeh Bishkul, Abolhassan Noori, Mohammad S. Rahmanifar, Nasim Hassani, Mehdi Neek-Amal, Junlei Liu, Cheng Zhang, Maher F. El-Kady, Nahla B. Mohamed, Richard B. Kaner, Mir F. Mousavi
Subnanoclusters
In article number 2507934, Abolhassan Noori, Richard B. Kaner, Mir F. Mousavi, and co-workers report a bio-inspired protein templated strategy to synthesize iron and nickel subnanoclusters with atomic precision, embedded in a graphene-derived porous framework. The resulting hybrid architecture delivers exceptional electrochemical performance for both energy storage and oxygen evolution. This work illustrates how molecular-level control can unlock new frontiers in sustainable energy technologies.
在文章编号2507934中，Abolhassan Noori, Richard B. Kaner, Mir F. Mousavi及其同事报道了一种生物启发蛋白质模板策略，以原子精度合成铁和镍的亚纳米簇，嵌入石墨烯衍生的多孔框架中。由此产生的混合结构为能量存储和氧气释放提供了卓越的电化学性能。这项工作说明了分子水平的控制如何开启可持续能源技术的新领域。
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Mixed polyester wastes with different chemical structures remain a key obstacle to achieving circularity in plastic utilization. Here, a programmable one‐pot photothermal strategy is reported using a catalyst derived from a bimetallic MOF (Zn/Co‐ZIF‐C) through pyrolysis of a Zn/Co‐integrated precursor. This system enables the efficient and sequential depolymerization of polycarbonate (PC), polylactic acid (PLA), and polyethylene terephthalate (PET) in mixed streams by simply tuning the irradiation intensity. Selective glycolysis of PC, PLA, and PET is triggered at ≈420, 520, and 650 mW cm −2 , respectively, enabling stepwise monomer recovery in a single reactor. Density functional theory calculations reveal a dual‐site cooperative mechanism, in which ZnO and Co‐N x sites cooperatively activate ester bonds and ethylene glycol, offering a mechanistic basis for the observed substrate‐specific reactivity. The Zn/Co‐ZIF‐C catalyst exhibits broadband light absorption, strong catalytic activity, and excellent recyclability, maintaining over 95% PET conversion across five cycles. Moreover, it achieves monomer yields above 80% from nine real‐world post‐consumer plastics, while simultaneously removing dyes and performing magnetic separation. This work presents a robust and scalable catalytic platform for light‐controlled, selective upcycling of complex polyester mixtures, offering new opportunities for sustainable plastic circularity.
具有不同化学结构的混合聚酯废料仍然是实现塑料循环利用的主要障碍。本文报道了一种可编程的单锅光热策略，该策略使用由双金属MOF （Zn/Co‐ZIF‐C）通过热解Zn/Co‐集成前驱体衍生的催化剂。该系统通过简单地调整辐照强度，实现了混合流中聚碳酸酯（PC）、聚乳酸（PLA）和聚对苯二甲酸乙二醇酯（PET）的高效和顺序解聚。PC， PLA和PET的选择性糖酵解分别在≈420,520和650 mW cm−2下触发，从而在单个反应器中实现单体的逐步回收。密度泛函理论计算揭示了ZnO和Co - N - x位点协同激活酯键和乙二醇的双位点协同机制，为观察到的底物特异性反应性提供了机制基础。Zn/Co - ZIF - C催化剂具有宽带光吸收、强催化活性和优异的可回收性，在5个循环中保持95%以上的PET转化率。此外，在去除染料和进行磁分离的同时，它可以从9种现实世界的消费后塑料中获得80%以上的单体收率。这项工作为复杂聚酯混合物的光控、选择性升级回收提供了一个强大的、可扩展的催化平台，为可持续塑料循环提供了新的机会。
{"title":"Programmable Photothermal Upcycling of Mixed Polyesters via Light‐Intensity Gating on a Bifunctional Zn/Co‐ZIF‐C Catalyst","authors":"Haoyi Wang, Le Xu, Chunying Si, Yankai Zhang, Yunbiao Qi, Quanxing Zhang, Wei Jiang","doi":"10.1002/smll.202513604","DOIUrl":"https://doi.org/10.1002/smll.202513604","url":null,"abstract":"Mixed polyester wastes with different chemical structures remain a key obstacle to achieving circularity in plastic utilization. Here, a programmable one‐pot photothermal strategy is reported using a catalyst derived from a bimetallic MOF (Zn/Co‐ZIF‐C) through pyrolysis of a Zn/Co‐integrated precursor. This system enables the efficient and sequential depolymerization of polycarbonate (PC), polylactic acid (PLA), and polyethylene terephthalate (PET) in mixed streams by simply tuning the irradiation intensity. Selective glycolysis of PC, PLA, and PET is triggered at ≈420, 520, and 650 mW cm <jats:sup>−2</jats:sup> , respectively, enabling stepwise monomer recovery in a single reactor. Density functional theory calculations reveal a dual‐site cooperative mechanism, in which ZnO and Co‐N <jats:italic>x</jats:italic> sites cooperatively activate ester bonds and ethylene glycol, offering a mechanistic basis for the observed substrate‐specific reactivity. The Zn/Co‐ZIF‐C catalyst exhibits broadband light absorption, strong catalytic activity, and excellent recyclability, maintaining over 95% PET conversion across five cycles. Moreover, it achieves monomer yields above 80% from nine real‐world post‐consumer plastics, while simultaneously removing dyes and performing magnetic separation. This work presents a robust and scalable catalytic platform for light‐controlled, selective upcycling of complex polyester mixtures, offering new opportunities for sustainable plastic circularity.","PeriodicalId":228,"journal":{"name":"Small","volume":"31 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nadine Denis, Akant Sagar Sharma, Elena Blundo, Francesca Santangeli, Paolo De Vincenzi, Riccardo Pallucchi, Mitsuki Yukimune, Alexander Vogel, Ilaria Zardo, Antonio Polimeni, Fumitaro Ishikawa, Marta De Luca
Bandgap engineering in semiconductors is required for the development of photonic and optoelectronic devices with optimized absorption and emission energies. This is usually achieved by changing the chemical or structural composition during growth or by dynamically applying strain. Here, the bandgap in GaAsN nanowires grown on Si is increased post‐growth by up to 460 meV in a reversible, tunable, and non‐destructive manner through H implantation. Such a bandgap tunability is unattained in epilayers and enabled by relaxed strain requirements in nanowire heterostructures, which enables N concentrations of up to 4.2% in core–shell GaAs/GaAsN/GaAs nanowires resulting in a GaAsN bandgap as low as 0.97 eV. Using ‐photoluminescence measurements on individual nanowires, it is shown that the high bandgap energy of GaAs at 1.42 eV is restored by hydrogenation through the formation of N–H complexes. By carefully optimizing the hydrogenation conditions, the photoluminescence efficiency increases by an order of magnitude. Moreover, by controlled thermal annealing, the large shift of the bandgap is not only made reversible but also continuously tuned by breaking up N–H complexes in the hydrogenated GaAsN. Finally, local bandgap tuning by laser annealing is demonstrated, opening up new possibilities for developing novel, locally and energy‐controlled quantum structures in GaAsN nanowires.
{"title":"Bandgap Engineering On Demand in GaAsN Nanowires by Post‐Growth Hydrogen Implantation","authors":"Nadine Denis, Akant Sagar Sharma, Elena Blundo, Francesca Santangeli, Paolo De Vincenzi, Riccardo Pallucchi, Mitsuki Yukimune, Alexander Vogel, Ilaria Zardo, Antonio Polimeni, Fumitaro Ishikawa, Marta De Luca","doi":"10.1002/smll.202506091","DOIUrl":"https://doi.org/10.1002/smll.202506091","url":null,"abstract":"Bandgap engineering in semiconductors is required for the development of photonic and optoelectronic devices with optimized absorption and emission energies. This is usually achieved by changing the chemical or structural composition during growth or by dynamically applying strain. Here, the bandgap in GaAsN nanowires grown on Si is increased post‐growth by up to 460 meV in a reversible, tunable, and non‐destructive manner through H implantation. Such a bandgap tunability is unattained in epilayers and enabled by relaxed strain requirements in nanowire heterostructures, which enables N concentrations of up to 4.2% in core–shell GaAs/GaAsN/GaAs nanowires resulting in a GaAsN bandgap as low as 0.97 eV. Using ‐photoluminescence measurements on individual nanowires, it is shown that the high bandgap energy of GaAs at 1.42 eV is restored by hydrogenation through the formation of N–H complexes. By carefully optimizing the hydrogenation conditions, the photoluminescence efficiency increases by an order of magnitude. Moreover, by controlled thermal annealing, the large shift of the bandgap is not only made reversible but also continuously tuned by breaking up N–H complexes in the hydrogenated GaAsN. Finally, local bandgap tuning by laser annealing is demonstrated, opening up new possibilities for developing novel, locally and energy‐controlled quantum structures in GaAsN nanowires.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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